ES2315236T3 - INCIDENT MOISTURE METHOD FOR OBTAINING CYANIDE CATALYSTS CONTAINING METAL. - Google Patents

Abstract

Metal cyanide catalysts are prepared by first forming a precipitate using no more than a stoichiometric amount of a water-soluble metal salt of the form MxAy, based on the amount of metal cyanide compound that is used. The precipitate is then treated with an additional quantity of a metal salt of the form M3xAy, in which M3 may be the same as or different than M. The catalyst is treated with a complexing agent, either during the precipitation step or during the subsequent treatment with the M3xAy salt.

Description

Incipient moisture method to obtain cyanide catalysts containing metal.

This invention relates to certain catalysts containing metals and methods for preparing catalysts containing metals for oxide polymerization of alkylene.

Alkylene oxides such as oxide ethylene, propylene oxide and 1,2-butylene oxide they polymerize to form a wide variety of type products polyether For example, polyether polyols are They prepare in large quantities for polyurethane applications. Other polyethers are used as lubricants, brake fluids, liquids for compressors and many other applications.

These polyethers are usually prepared polymerizing one or more alkylene oxides in the presence of a initiator compound and a catalyst. Recently, the so-called Double metal cyanide (DMC) catalysts Metal Cyanide) have been used commercially as catalysts for polymerization for alkylene oxides. These catalysts are described in, for example, US Pat. No. 3,278,457, 3,278,458, 3,278,459, 3,404,109, 3,427,256, 3,427,334, 3,427,335, 5,470,813 among many others. European patent application EP 0 755 716 describes a certain zinc hexacyanocobaltate catalyst containing less than 0.2 moles of zinc halide salt per mole of DMC compound Although these catalysts are described very widely in the patent literature, only one number limited forms of the catalyst have been shown to be catalysts of active alkylene oxide polymerization.

Activated catalysts are typically prepared by mixing an excess of a water soluble salt of a metal M with a water soluble compound containing an anion of the type M1 [(CN) r (X) t }], in aqueous solution. An excess of the M salt is essential to produce an active catalyst. In addition, the active forms of the catalyst all require the presence of an organic complexing agent. In conventional processes, this is achieved by adding the complexing agent to one or both of the starting solutions or by adding the complexing agent separately immediately after mixing the starting solutions. A catalyst complex containing the M b [M 1 (CN) r (X) t] c
insoluble, associated with the complexing agent and bound water, precipitates and is washed, usually multiple times, with mixtures of the complexing agent and water.

The preparation method described has several disadvantages First, the variety of compositions that can be obtaining is usually limited to those that have only one type of ion M.

Second, as the salt of the metal M is soluble in water, at least part of the excess salt remains in the phase aqueous when the catalyst complex precipitates first. This salt is It loses when the precipitated catalyst is isolated. So, some of the salt is lost, and unless the product is subsequently analyzed, It is often unknown how much of the excess salt is incorporated into the catalyst. This may be important, as it is believed that the activity of the catalyst complex depends on the presence of a excess salt

In addition, the preparation method described previously used much more compounding agent complexing than It really binds to the catalyst complex. This is the result higher raw material costs and increases the overall cost of the Obtaining the catalyst complex.

Thus, it would be desirable to provide a method for which can incorporate controlled amounts of metal salt in excess of a metal-containing cyanide catalyst. Further, it would be desirable to provide a less expensive method to obtain these catalyst complexes that contain metals, and reduce quantities of raw materials and the number of stages needed to Prepare these catalyst complexes.

In one aspect, this invention is a method for prepare a metal-containing catalyst, which comprises stages of:

to)

form a first dissolution of a metallic salt in water;

b)

form a second aqueous solution of a metal cyanide compound or a mixture thereof with a additional compound having an anion containing metal of transition, which forms an insoluble salt with the metal in said salt metallic;

C)

mix said first and second solutions in proportions such that no more than one is present stoichiometric amount of the metal salt in the mixture, referred to to the number of equivalents of the metal cyanide compound and any additional compound present, under conditions such that the metal salt, metal cyanide compound and compound additional, if present, react to form a insoluble precipitate;

where stage c) is carried out in the presence of an organic complexing agent compound, step c) is followed by washing the insoluble precipitate with an agent compound organic complexing, or both, after

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d)

remove excess water and any organic complexing agent in excess of insoluble precipitate to  form an isolated precipitate; Y

and)

mix the isolated precipitate with a impregnation solution containing an additional amount of a metal salt dissolved in water or a mixture of water and an agent soluble organic complexing, under conditions such that the impregnation solution is substantially absorbed by the isolated precipitate, where the concentration of the metal salt in the impregnation solution is such that 0.1 to 1.5 are provided moles of metal salt to said impregnation solution per mole of metal cyanide compound and anion containing metal transition in the isolated precipitate.

The method of the first aspect of the invention provides a convenient way to obtain complexes catalysts containing metals, which have a content controlled excess metal salt. The method also prevents or minimizes losses of metal salt during the stages of washed.

In another aspect, this invention is a method. to prepare a catalyst containing metal, which comprises the stages of:

to)

form a first dissolution of a metallic salt in water;

b)

form a second aqueous solution of a metal cyanide compound or a mixture thereof with a additional compound having an anion containing metal of transition, which forms an insoluble salt with the metal in said salt metallic;

C)

in substantial absence of an organic complexing agent, mix said first and second solutions in proportions such that no more than one stoichiometric amount of the metal salt is present in the reaction mixture, based on the number of equivalents of the metal cyanide compound and any additional compound present, under conditions such that the metal salt, the compound of metallic cyanide and the additional compound, if found present, they react to form an insoluble precipitate;

d)

remove excess water from insoluble precipitate to form an isolated precipitate;

and)

mix the isolated precipitate with a impregnation solution containing an additional amount of a metal salt dissolved in a mixture of water and an agent soluble organic complexing, under conditions such that the impregnation solution is substantially absorbed by the isolated precipitate, where the concentration of the metal salt in the impregnation solution is such that 0.1 to 1.5 are provided moles of metal salt to said impregnation solution per mole of metal cyanide compound and anion containing metal transition in the isolated precipitate.

This second aspect of the invention provides a method by which a cyanide catalyst can be prepared containing metal, highly active, using a reduced amount of organic complexing agent and with an excess of the metal salt easily controlled. The activity of this catalyst is particularly surprising since conventional methods of preparation of catalysts containing metals require the addition of large amounts of complexing agent during initial precipitation of the catalyst complex.

In addition, this method provides a convenient way of obtaining specialized catalyst complexes, since different metal salts can be used to obtain the initial precipitate and in the impregnating solution.
tion.

In a third aspect, this invention is a method of preparing a metal containing cyanide catalyst, which comprises the stages of:

to)

form a first dissolution of a metallic salt in water;

b)

form a second aqueous solution of a metal cyanide compound or a mixture thereof with a additional compound having an anion containing metal of transition, which forms an insoluble salt with the metal in said salt metallic;

C)

mix said first and second solutions in proportions such that no more than one is present stoichiometric amount of the metal salt in the mixture of reaction, referring to the combined number of equivalents of the metal cyanide compound and additional compound, if any, in conditions such that the metal salt, the cyanide compound metallic and the additional compound, if present, they react to form an insoluble precipitate;

d)

remove excess water from insoluble precipitate to form an isolated precipitate; Y

and)

mix the isolated precipitate with a impregnation solution containing an additional amount of a metal salt dissolved in a mixture of water and an agent soluble organic complexing, where the salt concentration metallic in the impregnation solution is such that they are provided 0.1 to 1.5 moles of metal salt to said impregnation solution per mole of metal cyanide compound and metal containing anion of transition in the isolated precipitate.

The metal-containing cyanide catalyst, prepared by the method of this invention can be represented by The general formula:

M_ {b} [M 1} (CN) r (X) t] c [M 2 (X) 6] d • zL \ cdot aH_ {2} O \ cdot nM3 {} x A_,

in the that

M is a metal ion that forms a precipitate insoluble with the group M 1 (CN) r (X) t, and having at least one water soluble salt;

M 1 and M 2 are metal ions of transition that may be the same or different;

each X independently represents a group other than cyanide that coordinates with an M 1 or M 2 ion;

L represents an organic complexing agent;

M 3 x A y represents a soluble salt in metal ion water M3 and anion A;

b and c are positive numbers that, together with d, they reflect an electrostatically neutral complex;

d is zero or a positive number;

x e y are numbers that reflect a salt electrostatically neutral;

r is from 4 to 6; t is 0 to 2; Y

z, a and n are positive numbers (which can be fractions) indicating the relative amounts of the agent complexing, water molecules and M 3 x A y, respectively.

X groups in any M 2 (X) 6 does not have to be all the same. The molar ratio of c: d is advantageously, from 100: 0 to 20:80, more preferably from 100: 0 to 50:50 and even more preferably from 100: 0 to 80:20.

The expression "metal salt" is used in this memory to refer to a salt of formula M_ {x} A_ {y} or M 3 x A y, where M, M 3, x, A and y are as defined above.

M and M3 are preferably metal ions selected from the group consisting of Zn + 2, Fe + 2, Co + 2, Ni + 2, Mo + 4, Mo + 6, Al + 3, V + 4, V + 5, Sr + 2, W + 4, W + 6, Mn + 2, Sn + 2, Sn + 4, Pb + 2, Cu + 2, La + 3 and Cr + 3. M and M3 they are more preferably Zn + 2, Fe + 2, Co + 2, Ni + 2, La + 3 and Cr + 3. M is most preferably Zn + 2.

Suitable anions A include halides such as chloride and bromide, nitrate, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, perchlorate, isothiocyanate and a carboxylate C_ {1-4}. Ion is especially preferred chloride.

The expression "cyanide compound metallic "is used herein to refer to a compound as the one represented by the structure B u [M 1 (CN) r (X) t] v, where B represents hydrogen or a metal atom that forms a salt water soluble with the group M 1 (CN) r (X) t, u and v are integers that reflect an electrostatically neutral salt and M1, r, X and t are as defined above. B is preferably hydrogen or an alkali metal such as lithium, potassium, sodium or cesium.

The term "additional compound" is used in this report to refer to a compound that has the general structure B u [M 2 (X) 6] v, where B, M2, X, u and v are as defined above. The use of an additional compound is optional in this invention.

M 1 and M 2 are preferably Fe + 3, Fe + 2, Co + 3, Co + 2, Cr + 2, Cr + 3, Mn + 2, Mn + 3, Ir + 3, Ni + 2, Rh + 3, Ru + 2, V + 4 and V + 5. Among the above, the most preferred are those They have an oxidation state +3. Co + 3 and Fe + 3 are even more preferred and Co + 3 is the most preferred.

Preferred X groups include such anions as halide (especially chloride), hydroxide, sulfate, carbonate, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate C 1-4 and nitrite (NO 2 -), and non-species loaded such as CO, H2O and NO. X groups particularly Preferred are NO, NO 2 - and CO.

The catalyst is complexed with an agent organic complexing A large number of complexing agents are potentially useful, although catalyst activity can vary according to the selection of a particular complexing agent. Examples of such complexing agents include alcohols, aldehydes, ketones, ethers, amides, nitriles and sulfides.

Suitable alcohols include monoalcohols and polyols. Suitable monoalcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, octanol, octadecanol, 3-butin-1-ol, 3-butene-1-ol, propargyl alcohol, 2-methyl-2-propanol, 2-methyl-3-butin-2-ol, 2-methyl-3-butene-2-ol, 3-butin-1-ol, 3-butene-1-ol, and 1-t-butoxy-2-propanol. Suitable monoalcohols also include halogenated alcohols such as 2-chloroethanol, 2-bromoethanol, 2-chloro-1-propanol, 3-chloro-1-propanol, 3-bromo-1-propanol, 1,3-dichloro-2-propanol, 1-Chloro-2-methyl-2-propanol  as well as nitroalcohols, keto-alcohols, ester alcohols, cyanoalcohols, and other alcohols inertly substituted.

Suitable polyols include ethylene glycol, propylene glycol, glycerin, 1,1,1-trimethylol propane, 1,1,1-trimethylol-ethane, 1,2,3-trihydroxybutane, pentaerythritol, xylitol, arabitol, mannitol, 2,5-dimethyl-3-hexin-2,5-diol, 2,4,7,9-tetramethyl-5-decino-4,7-diol,  sucrose, sorbitol, alkyl glycosides such as methyl glycoside and ethyl glycoside. Low molecular weight polyether polyols, in particularly those that have an equivalent weight of 350 or less, more preferably 125-250, they are also agents useful complexing

Suitable aldehydes include formaldehyde, acetaldehyde, butyraldehyde, valeric aldehyde, glyoxal, benzaldehyde, and toluic aldehyde. Suitable ketones include acetone, methyl ethyl ketone, 3-pentanone, and 2-hexanone.

Suitable ethers include cyclic ethers such as dioxane, trioxymethylene and paraformaldehyde as well as acyclic ethers such as diethyl ether, 1-ethoxy-pentane, bis (betachloroethyl) ether, methyl propyl ether, diethoxy methane, dialkyl ethers of alkylene- or polyalkylene glycols (such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dimethyl ether of triethylene glycol and dimethyl ether of octaethylene glycol).

Amides such as formamide, acetamide, propionamide, butyramide and valeramide are complexing agents tools. Esters such as amyl formate, ethyl formate, hexyl formate, propyl formate, ethyl acetate, acetate of methyl, and triethylene glycol diacetate can also be used. Suitable nitriles include acetonitrile and proprionitrile. Sulphides Suitable include dimethyl sulfide, diethyl sulfide, sulfide of dibutyl, and diamyl sulfide.

Preferred complexing agents are t-butanol, 1-t-butoxy-2-propanol, polyether polyols having an equivalent weight of 75-350 and dialkyl ethers of alkylene and polyalkylene glycols. Especially preferred complexing agents are t-butanol, 1-t-butoxy-2-propanol, polyether polyols having an equivalent weight of 125-250 and a dimethyl ether of mono-, di- or triethylene glycol. Most preferred are t-butanol and glyme (1,2-dimethoxyethane).

In addition, the catalyst complex contains a amount of water that is linked to the crystalline network of the complex. Although the amount of bound water is difficult to determine, it is believed that this amount is 0.25 to 3 moles of water per mole of ions M 1 and M 2.

In the method of the first aspect of the invention, different aqueous solutions of the metal salt and the metal cyanide compound. Aqueous solutions can contain, in addition to water and metal salt or the compound of metallic cyanide, an amount of a mineral acid or a buffer for adjust the pH of the solution to more easily dissolve the salt metallic and metal cyanide compounds. In the first aspect of the invention, either or both of the solutions can contain an organic complexing agent or a polyether compound, as described above.

In this first aspect, the dissolution of the salt metal and the solution of the metal cyanide compound (which optionally contains an additional compound) are then mixed with agitation to proportions such that no more than one stoichiometric amount of metal salt, referred to equivalents of the metal cyanide compound (and compound additional, if present). The solutions can be Mix in any order. However, it is more preferred to add the dissolution of the metal cyanide compound to that of the salt metallic This tends to reduce the amount of unwanted ions that They are trapped in the complex. By quantity stoichiometric ", it is understood that the metal salt is found present in an excess of not more than 5% in equivalents, preferably in an excess not exceeding 2% in equivalents, more preferably in an excess not exceeding 1% in equivalents, referred to the amount of metal cyanide compound plus Any additional compound. Most preferred is that the number of metal salt equivalents is approximately equal to the number of metal cyanide compound equivalents, plus any Additional compound that may be present.

When the solutions are mixed, a precipitate. The precipitate corresponds to the structure M_ [M 1 (CN) r (X) t] c [M 2 (X) 6] d,  ? aH2O where M, M1, X, a, b, c, d, r and t are as It has been defined above. If one or both of the solutions Starting contain an organic complexing agent, the precipitate it will also contain a number of complexing agent molecules linked.

The resulting precipitate is isolated after water by filtration, centrifugation or other suitable process. In the first aspect of the invention, preferably the precipitated one or more times with water to remove ions occluded such as those designated by B and X in the formulas previous. It is particularly preferred to remove any ions of halide and alkali metal of the precipitated complex up to level as low as reasonably possible. In the method of first aspect of the invention, if none of the solutions of heading contains an organic complexing agent, one or more of the subsequent washings must contain an amount of the agent complexing However, if the complexing agent is found present in one or both of the starting solutions, its use is optional in subsequent washings. When an agent is used complexing in the washings, this advantageously constitutes from 10 to 100 percent by weight of the wash solution. A method convenient to carry out the washings, is to wash the precipitate multiple times, gradually increasing the agent content complexing of the washing solution, so that the washing final is 100 percent by weight, complexing agent.

Then, the precipitate is dried to remove the excess water, and excess complexing agent if one or more of The washes also contains the complexing agent. This is done conveniently heating the precipitate in vacuo to a somewhat elevated temperature, such as 35 to 95 ° C, preferably 45-75 ° C, until the precipitate reaches a weight constant. The resulting product is the isolated precipitate.

Then, the isolated precipitate is impregnated with a solution of a metal salt, M 3 x A y, in water. In the first aspect of the invention, this dissolution of impregnation may also contain one or more compound agents complexing The impregnation solution may also contain, if desired, a polyether, especially a poly (propylene oxide) of molecular weight up to 4000. Impregnation is easily done with simple mixing at any convenient temperature, preferably room temperature. Enough of the dissolution of impregnation is used to provide a sufficient amount of the metal salt to form an active catalyst complex. Typically, from 0.1, preferably from 0.25 to 1.5, preferably to 1.0, more preferably 0.75, moles of excess metal salt per mole of ion M1 and M2 is sufficient to form a active complex. When M 3 x A y is zinc chloride, these amounts correspond to 9 to 30, preferably 11 to 25, parts by weight of zinc chloride per 100 parts by weight of isolated precipitate.

In addition, it is preferred that the amount does not exceed the amount of solution that can be substantially absorbed by the precipitate The amount of solution that can be absorbed will vary according to the chemical composition of the isolated precipitate and of its porosity A typical amount of solution to be used is from 0.5 to 2, preferably 0.8 to 1.5, more preferably 1 to 1.5, milliliters of solution per gram of isolated precipitate.

In the first aspect of the invention, the impregnation solution advantageously contains water and agent complexing in a weight ratio of 100: 0 to 10:90, preferably 90:10 to 30:70.

It is noted that the metal salt used in the impregnation solution does not have to be the same metal salt which is used in the initial stage of precipitation. In particular, the respective metal salts may contain different metals. Thus, for example, a zinc salt can be used at the stage of precipitation, but in the impregnation stage a salt of lanthanum, chromium, iron or other metal. How can they be used? different metal salts in the method of the invention, this method provides a method by which, the catalyst complexes are They can adapt for specific applications.

After mixing the isolated catalyst with the impregnation solution, the mixture typically has a thick consistency of mud type.

The method of the first aspect of the invention provides the advantages of allowing the amount of salt to be controlled excess metal introduced into the catalyst complex and in some cases reduce the amount of metal salt that is needs to.

The second aspect of the invention is similar, except that no complexing agent is introduced into the system until that the impregnation solution is added to the isolated precipitate. That is, none of the starting solutions contains an agent. organic complexing, and preferably does not contain a polyether or other organic species, either. The precipitate that forms at from the solutions thereof it is substantially free of organic complexing agent. In addition, in the second aspect of the invention, the following washings of the precipitate are made with a washing solution lacking a complexing agent, polyether polyol and other organic species, so that the isolated precipitate remains substantially free of those materials.

In the method of the second aspect, the dissolution impregnation contains, in addition to water and metal salt, a amount of organic complexing agent and optionally a polyether or other desirable organic species. In this second aspect, the impregnation solution advantageously contains water and agent complexing in a weight ratio of 90:10 to 10:90, preferably 70:30 to 30:70. As before, it is preferred that it is no longer used solution that can be absorbed substantially by the isolated precipitate.

The second aspect method provides the additional advantages of substantially reducing the amount of complexing agent that is used in the process, and to simplify the catalyst preparation As the first aspect method, the second aspect method provides controlled introduction of predetermined amounts of excess metal salts in the catalyst complex

In any aspect of the invention, the impregnated catalyst is preferably allowed to stand in conditions close to environmental conditions (ambient temperature, atmospheric pressure) over a period to allow salt metal and the complexing agent bind to the catalyst complex. This process is typically completed in a few hours in environmental conditions. If desired, temperatures can be applied slightly elevated and / or slightly low pressures to accelerate the process. Then, preferably, the catalyst is dried at vacuum and / or higher temperatures to complete the process of dried

In addition, in any aspect of the invention, the impregnation stage can be carried out in two or more stages. Thus, after carrying out a first impregnation stage, it is left that the complexing agent binds to the complex, and the complex as before. Then, a second one is carried out impregnation stage and the catalyst is treated and dried as it is described above More stages of impregnation in a similar manner. The use of multiple impregnations is desirable when a high load of M 3 x A y, or when the M 3 x A y is nothing soluble in the impregnation solution.

Preferred catalysts that can be Prepare by the methods of the invention include:

Zinc Hexacyanocobaltate \ zd \ cdot aH 2 O • nZnCl 2;

Zn [Co (CN) 5 NO] \ cdot zL • aH 2 O • nZnCI_ {2};

Zn_ {s [Co (CN) 6] o [Fe (CN) 5 NO] p \ cdot zL \ cdot t aH_ {2} O \ cdot nZnCL_ {2} (or, p = numbers positive, s = 1.5o + p);

Zn_ {s} [Co (CN) 6] o [Co (NO 2) 6] p [Fe (CN) 5 NO] q \ cdot zL \ cdot aH_ {2} O \ cdot nZnCL_ {2} (o, p, q = numbers positive, s = 1.5 (o + p) + q);

Zinc Hexacyanocobaltate \ zd \ cdot t aH 2 O • nLaCl 3;

Zn [Co (CN) 5 NO] \ cdot zL • aH 2 O • nLaCI_ {3};

Zn [Co (CN) 6] o [Fe (CN) 5 NO] p \ cdot zL \ cdot aH_ {2} O \ cdot nLaCI_ {3} (or, p = numbers positive, s = 1.5o + p);

Zn_ {S} [Co (CN) 6] o [Co (NO 2) 6] p [Fe (CN) 5 NO] q \ cdot zL \ cdot aH_ {2} O \ cdot nLaCI_ {3} (o, p, q = numbers positive, s = 1.5 (o + p) + q);

Zinc Hexacyanocobaltate \ zd \ cdot aH 2 O • nCrCI 3;

Zn [Co (CN) 5 NO] \ cdot zL • aH 2 O • nCrCI_ {3};

Zn_ {s} [Co (CN) 6] o [Fe (CN) 5 NO] p \ cdot zL \ cdot aH_ {2} O \ cdot nCrCl_ {3} (or, p = numbers positive, s = 1.5o + p);

Zn_ {s} [Co (CN) 6] o [Co (NO 2) 6] p [Fe (CN) 5 NO] q \ cdot zL \ cdot aH_ {2} O \ cdot nCrCl_ {3} (o, p, q = numbers positive, s = 1.5 (o + p) + q);

Magnesium hexacyanocobaltate \ zd • aH 2 O • nZnCI_ {2};

Mg [Co (CN) 5 NO] • zL • aH 2 O • nZnCI_ {2};

Mg S [Co (CN) 6] o [Fe (CN) 5 NO] p \ cdot zL \ cdot aH_ {2} O \ cdot nZnCI_ {2} (or, p = numbers positive, s = 1.5o + p);

Mg S Co (CN) 6] o [Co (NO 2) 6] p [Fe (CN) 5 NO] q \ cdot zL \ cdot aH_ {2} O \ cdot nZnCI_ {2} (o, p, q = numbers positive, s = 1.5 (o + p) + q);

Magnesium hexacyanocobaltate \ zd • aH 2 O • nLaCI_ {3};

Mg [Co (CN) 5 NO] • zL • aH 2 O • nLaCI_ {3};

Mg S [Co (CN) 6] o [Fe (CN) 5 NO] p \ cdot zL \ cdot aH_ {2} O \ cdot t nLaCI_ {3} (or, p = numbers positive, s = 1.5o + p);

Mg_s [Co (CN) 6] o [Co (NO2) 6] p [Fe (CN) 5 NO] q \ cdot zL \ cdot aH_ {2} O \ cdot nLaCI_ {3} (o, p, q = numbers positive, s = 1.5 (o + p) + q);

Magnesium hexacyanocobaltate \ zd • aH 2 O • nCrCI_ {3};

Mg [Co (CN) 5 NO] • zL • aH 2 O • nCrCI_ {3};

Mg_s [Co (CN) 6] o [Fe (CN) 5 NO] p \ cdot zL \ cdot aH_ {2} O \ cdot nCrCl_ {3} (or, p = numbers positive, s = 1.5o + p);

Mg_s [Co (CN) 6] o [Co (NO 2) 6] p [Fe (CN) 5 NO] q \ cdot zL \ cdot aH_ {2} O \ cdot nCrCI_ {3} (o, p, q = numbers positive, s = 1.5 (o + p) + q);

as well as the various complexes such as described in column 3 of US Pat. No. 3,404,109.

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The catalyst complex of the invention is used. to polymerize alkylene oxides to obtain polyethers. In In general, the process includes mixing a quantity catalytically Effective catalyst with an alkylene oxide under conditions of polymerization and let the polymerization run until the alkylene oxide supply is essentially over. The catalyst complex concentration is selected for polymerize the alkylene oxide at a desired rate or within of a desired period of time. The amount of complex catalyst is conveniently expressed in terms of its weight in parts per million of the polyether product. Product weight polyether is generally considered as weight Combined initiator plus monomers. Thus, an adequate amount of catalyst is 5 to 10,000 parts by weight of catalyst complex by combined weight in parts per million alkylene oxide, and initiator and comonomers, if any. The catalyst levels plus Preferred are 10, especially 25, to 500, more preferably 100 ppm, most preferably 50 ppm, therein base.

To obtain monofunctional polyethers of high molecular weight, it is not necessary to include a compound initiator. However, to control the molecular weight, confer desired functionality (number of groups hydroxyl / molecule) or a desired functional group, preferably mix an initiator compound with the catalyst complex at reaction start Suitable initiator compounds include monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, octanol, octadecanol, 3-butin-1-ol, 3-butene-1-ol, propargyl alcohol, 2-methyl-2-propanol, 2-methyl-3-butin-2-ol, 2-methyl-3-butene-2-ol,  3-butin-1-ol and 3-butene-1-ol. The suitable monoalcohol initiating compounds include halogenated alcohols such as 2-chloroethanol, 2-bromoethanol, 2-chloro-1-propanol, 3-chloro-1-propanol, 3-bromo-1-propanol, 1,3-dichloro-2-propanol, 1-Chloro-2-methyl-2-propanol Y 1-t-butoxy-2-propanol, as well as nitroalcohols, keto-alcohols, ester alcohols, cyanoalcohols, and other alcohols inertly substituted. Suitable polyalcohol type initiators include ethylene glycol, propylene glycol, glycerin, 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, 1,2,3-trihydroxybutane, pentaerythritol, xylitol, arabitol, mannitol, 2,5-dimethyl-3-hexin-2,5-diol, 2,4,7,9-tetramethyl-5-decino-4,7-diol,  sucrose, sorbitol, alkyl glycosides such as methyl glycoside and ethyl glycoside. However, the catalyst tends to behave better when the initiator is a polyether polyol, particularly one having an equivalent weight of 350 or less, more preferably 125-250.

Among the alkylene oxides that can be polymerize with the catalyst complex of the invention are rust of ethylene, propylene oxide, oxide 1,2-butylene, styrene oxide and mixtures thereof. Be they can sequentially polymerize various alkylene oxides to obtain block copolymers. More preferably, the oxide of alkylene is propylene oxide or a mixture of oxide of propylene and ethylene oxide and / or butylene oxide. It preferred especially propylene oxide alone or a mixture of at least 50 percent by weight of propylene oxide and up to 50 percent in ethylene oxide weight.

In addition, monomers can be used that they will copolymerize with the alkylene oxide in the presence of the complex catalyst for preparing polyether polyols modified. Such comonomers include oxetanes as described. in U.S. Pat. No. 3,278,457 and 3,404,109 and anhydrides as described in US Pat. No. 5,145,883 and 3,538,043, which give polyethers and polyester or polyether ester polyols, respectively. The hydroxyalkanoates such as lactic acid, 3-hydroxybutyrate, 3-hydroxyvalerate (and its dimers), lactones and carbon dioxide are examples of other suitable monomers that can be polymerized with the catalyst of the invention.

The polymerization reaction proceeds typically well at temperatures of 25 to 150 ° C or higher, preferably from 90-130 ° C. A technique of convenient polymerization involves mixing the catalyst complex e initiator, and pressurize the reactor with the oxide of alkylene The polymerization takes place after a short period of induction as indicated by the loss of pressure in the reactor. Induction periods of less than one minute to 20 are usually seen minutes and induction periods are often less than 15 minutes Once the polymerization has begun, conveniently additional alkylene oxide is fed to the reactor on demand until enough alkylene oxide has been added to produce a polymer of the desired equivalent weight.

Another convenient polymerization technique is a continuous method. In such continuous processes, an activated catalyst / initiator mixture is continuously fed to a continuous reactor such as a continuously stirred tank reactor (CSTR) or a tubular reactor. An alkylene oxide feed is introduced into the reactor and the product is continuously separated.

The catalyst of this invention is especially useful for obtaining homopolymers of propylene oxide and random copolymers of propylene oxide and up to 15 percent by weight of ethylene oxide (referred to all monomers). The polymers of particular interest have an equivalent weight of 800 hydroxyl, preferably 1000 to 5000, preferably 4000, more preferably at 2500, and an unsaturation of no more than 0.02 meq / g, preferably not more than 0.01 meq / g.

The polymeric product may have various uses, depending on its molecular weight, equivalent weight, functionality and the presence of any functional groups. The polyether polyols thus obtained are useful as Raw materials to obtain polyurethanes. Polyethers too can be used as surfactants, hydraulic fluids, such as raw materials to obtain surfactants and as materials of heading to obtain amino polyethers, among other uses.

The following examples are provided for illustrate the invention, but are not intended to limit its scope. TO Unless otherwise indicated, all parts and percentages They are by weight.

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Example 1 A. Catalyst Preparation

A solution of zinc chloride is prepared (4,937 parts) in water (100,813 parts) and HCl (added as eight 1M HCl drops).

A second solution of 8.018 is prepared parts of K 3 Co (CN) 6 in 157.86 parts of Water. The molar ratio of ZnCI_ {2} to K 3 Co (CN) 6 in the two solutions is 3: 2

The zinc chloride solution is placed in a vessel provided with a stirrer, and the dissolution of K 3 Co (CN) 6 is pumped into it at the speed of 2 ml / minute. A precipitate of Zn_3 [Co (CN) 6] 2. Be centrifuge the mixture until a liquid can be poured transparent supernatant The recovered precipitate is washed five times with about 150 parts of water, and centrifuged. He centrifuged precipitate is then dried in a vacuum oven (0.5 torr (65 Pa), 65 ° C overnight. The resulting product is later called stoichiometric precipitate A.

An impregnation solution is prepared dissolving 0.3 parts of zinc chloride in 2,242 parts of a 50/50 weight mixture of t-butanol and water deionized This solution is used to impregnate 1.5 parts of stoichiometric precipitate A. The impregnation is carried out mixing the stoichiometric precipitate A and the solution of impregnation and letting it stand at room temperature for approximately 90 minutes, followed by vacuum drying (0.5 torr (65 Pa), 65 ° C) for approximately 2.5 hours. The resulting product  Catalyst complex 1 is designated.

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B. Polymerization of propylene oxide

The activity of catalyst complex 1 is evaluates combining 0.0405 parts of it with 10.3 parts of a initiator (a poly (propylene oxide) of molecular weight 700 nominally trifunctional), and then react this mixture with propylene oxide. The catalyst and the initiator are loaded into a suitable reactor, and the reactor is purged with nitrogen. After it is heated to 110 ° C and pressurized to 40 psig (275 kPa) with propylene Then, propylene oxide is fed on demand, limited by the feed pumping speed, until Approximately 29 parts of propylene oxide have been fed. An induction period of 25 minutes is observed at the beginning of the reaction, point at which an exotherm takes place followed by rapid polymerization of the remaining propylene oxide.

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Example 2

The catalyst complex 2 is obtained by mixing 1.02 parts of stoichiometric precipitate A and 1.18 parts of a solution obtained by dissolving 0.248 parts of FeCl 3 in 1.76 g parts of a 50/50 weight mixture of t-butanol in water The mixture is allowed to stand at room temperature and then it is dried in the manner described in example 1.

The activity of the catalyst complex is evaluated 2 in the manner described in Example 1. They polymerize approximately  29 parts of propylene oxide in approximately 8 hours.

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Example 3

The catalyst complex 3 is obtained by mixing 1,029 parts of stoichiometric precipitate A and 1.62 parts of a solution obtained by dissolving 0.253 parts of LaCl 3 in 1,747 g parts of a 50/50 mixture by weight of t-butanol in water. The mixture is allowed to stand room temperature and then dried in the manner described in the Example 1.

The activity of the catalyst complex is evaluated 3 in the manner described in example 1. A period of induction of 42 minutes at the beginning of the reaction, at which point an exotherm takes place followed by rapid polymerization of the oxide of remaining propylene.

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Example 4

The catalyst complex 4 is obtained by mixing 1,044 parts of stoichiometric precipitate A and 2,026 parts of a solution obtained by dissolving 0.248 parts of CrCl 3 • 6 O 2 in 1,778 g parts of a mixture 50/50 by weight of t-butanol in water. Let stand the mixture at room temperature and then dried the way described in example 1.

The activity of the catalyst complex is evaluated 4 in the manner described in example 1. A period of 20 minute induction at the beginning of the reaction, at which point an exotherm takes place followed by rapid polymerization of the oxide of remaining propylene.

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Example 5

1,008 parts of precipitate are mixed stoichiometric A, 0.209 parts of Mg (OH) 2 and about 20 parts of water, and stir at temperature ambient for about 3 days to exchange a part of the zinc ions in the precipitate with magnesium ions. After, The sample is centrifuged to separate the solids. The liquid phase, and the water evaporates at room temperature. Be recover a solid (0.615 parts), which is believed to contain Mg 3 [Co (CN) 6] 2. This precipitate is the stoichiometric precipitate B.

An impregnation solution is prepared mixing 0.161 parts of zinc chloride in 1,116 parts of a 50/50 mixture by weight of t-butanol and water. He stoichiometric precipitate B is impregnated with this solution of impregnation, dried at room temperature and then in an oven under vacuum (0.5 torr (65 Pa), 65 ° C) to dryness approximately constant. The product is designated catalyst complex 5.

The activity of the catalyst complex is evaluated 5 in the manner described in example 1. A period of induction of 87 minutes at the beginning of the reaction, at which point an exotherm takes place followed by rapid polymerization of the oxide of remaining propylene.

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Example 6

The catalyst complex 6 is obtained by mixing 0.5 parts of stoichiometric precipitate A and 0.50 parts of a solution obtained by dissolving 0.22 parts of zinc chloride in 1.00 parts of a 50/50 mixture by volume of t-butanol in water. The mixture is allowed to stand room temperature and then dried in the manner described in the Example 1.

The activity of the catalyst complex is evaluated 6 adding 0.04 parts of the catalyst and 9.88 parts of a poly (propylene oxide) of molecular weight 700, nominally Trifunctional to a small reactor. The reactor is heated to 110 ° C and Pressurized to 40 psig (275 kPa) with propylene oxide. Later feeds the reactor propylene oxide on demand until they have been consumed 33 parts. The reaction mixture is then transferred to a larger stirred vessel, heated to 110 ° C and pressurized at 40 psig (275 kPa) with propylene oxide. Then he feeds Propylene oxide on demand until 166 parts have been consumed More propylene oxide. An induction period is observed at beginning of the reaction, at which point an exotherm takes place followed by rapid polymerization of the remaining propylene oxide. The product has an Mn of 16,297, an Mw of 27,045, a% of OH of 0.39 and 0.013 meq / g unsaturation.

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Example 7

The catalyst complex 7 is obtained by mixing 0.5 parts of stoichiometric precipitate A and 0.68 parts of a solution obtained by dissolving 0.08 parts of zinc chloride in 0.6 parts of a 50/50 mixture by volume of t-butanol in water. The mixture is allowed to stand room temperature and then dried in the manner described in the Example 1.

The activity of the catalyst complex is evaluated 7 in the manner described in example 1. A period of induction of 76 minutes at the beginning of the reaction, at which point an exotherm takes place followed by rapid polymerization of the oxide of remaining propylene.

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Example 8

The catalyst complex 8 is obtained suspending 0.5 parts of stoichiometric precipitate A in 5 ml of t-butanol. The suspension is stirred at temperature Ambient for about an hour. Then, a 0.2 parts solution of zinc chloride in 1 ml of a mixture to 80/20 of t-butanol in water. Let the mix at room temperature and then dry the way described in example 1. A white powder is obtained.

The activity of the catalyst complex is evaluated 8 in the manner described in example 1. A period of 23-minute induction at the beginning of the reaction, at which point an exotherm takes place followed by rapid polymerization of the oxide of remaining propylene.

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Example 9

The catalyst complex 9 is obtained by mixing 1,012 parts of stoichiometric precipitate A and 2,183 parts of a solution obtained by dissolving 0.292 parts of zinc chloride in 2,266 parts of a 50/50 weight mixture of glyme (1,2-dimethoxyethane) in water. Let the mix at room temperature for about four hours and then dried under vacuum (0.5 torr (65 Pa)) at approximately 65 ° C for about 2 hours.

The activity of the catalyst complex is evaluated 9 in the manner described in example 1. A period of 49-minute induction at the beginning of the reaction, at which point an exotherm takes place followed by rapid polymerization of the oxide of remaining propylene.

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Example 10

8.0 parts of K 3 Co (CN) 6 in 150 parts of water. Is obtained a solution other than 4.92 parts of zinc chloride in 30 water parts The solutions are mixed in a mixer, followed by the addition of 130 parts of a 44/56 solution in t-butanol weight in water. The product is centrifuged  to isolate precipitated solids. The isolated solids are mixed with 130 parts of a 64/36 mixture by weight of t-butanol and water and centrifuged again. The solids thus obtained are mixed with 77 parts of t-butanol, centrifuged and dried under vacuum at 60 ° C

1.25 parts of the dried solids are homogenized in 130 parts of a 44/56 solution of t-butanol / water, to form a suspension. Be dissolve 1.5 parts of zinc chloride in 5 parts of water, add to the homogenized suspension and mix at speed raised for 3 minutes. The resulting dispersion is centrifuged, and the solids are mixed with 130 parts of a 64/36 solution of t-butanol in water. The product is centrifuged, and The solids are mixed with 77 parts of t-butanol. The product is centrifuged again and dried under vacuum at 60 ° C for 6 hours to produce the catalyst complex 10. Analysis by neutron activation on catalyst complex 10 sample 25.6% zinc, 14.8% cobalt and 0.9% potassium.

The activity of the catalyst complex is evaluated 10 in the manner described in example 1. A period of 20 minute induction at the beginning of the reaction, at which point an exotherm takes place followed by rapid polymerization of the oxide of remaining propylene.

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Example 11

0.996 parts of precipitate are treated stoichiometric A with 0.103 parts of LaCI 3 dissolved in 1,995 parts of a 50/50 weight mixture of water and t-butanol. The pasty type product is dried at room temperature for several hours. Then they come back to impregnate with a solution of 0.075 parts of LaCI 3 in 0.700 parts of a 50/50 weight mixture of water and t-butanol. Then the catalyst complex is dried for two days at room temperature and dried under vacuum at 140 ° C and 0.5 torr (65 Pa) for 30 hours.

Claims (24)

1. A method to prepare a catalyst that It contains metal, which comprises the stages of: a) form a first solution of a salt metallic in water; b) forming a second aqueous solution of a metal cyanide compound or a mixture thereof with a additional compound having an anion containing metal of transition, which forms an insoluble salt with the metal in said salt metallic; c) mixing said first and second solutions in proportions such that no more than one quantity is present stoichiometric metal salt in the reaction mixture, referred to the combined number of equivalents of the compound of metallic cyanide and any additional compound present, in conditions such that the metal salt, the cyanide compound metallic and the additional compound, if present, they react to form an insoluble precipitate; where optionally (i) step c) takes conducted in the presence of an organic complexing agent compound and / or (ii) step c) is followed by the washing of the insoluble precipitate with the organic complexing agent compound; d) separate the water in excess and, when the organic complexing agent has been added in said optional step (s) (i) and / or (ii), any organic complexing agent in excess of the precipitate insoluble to form an isolated precipitate; Y e) mix the isolated precipitate with a impregnation solution containing an additional amount of a metal salt dissolved in a mixture of water and an agent soluble organic complexing, or optionally, when added an organic complexing agent in said step (s) optional (s) (i) and / or (ii), in water, under conditions such that the impregnation solution is substantially absorbed by the isolated precipitate, where the concentration of the metal salt in the impregnation solution is such that 0.1 to 1.5 are provided moles of metal salt to said impregnation solution per mole of metal cyanide compound and anion containing metal transition in the isolated precipitate. 2. A method according to claim 1, wherein the step c) is carried out in the presence of an agent compound organic complexing, stage c) is followed by washing Insoluble precipitate with an organic complexing agent compound, or both and the impregnation solution contains the amount additional of a metal salt dissolved in water or in a mixture of water and a soluble organic complexing agent. 3. A method according to claim 1, wherein the step c) is carried out in the substantial absence of an agent organic complexing 4. A method according to any one of the previous claims, wherein the metal of the metal salt in the impregnation solution it is the same as in the first dissolution. 5. A method according to any one of the claims 1 to 3, wherein the metal of the metal salt in the impregnation solution is different from the first dissolution. 6. A method according to any of the previous claims, wherein the catalyst containing Metal is represented by the general formula: M_ {b} [M 1} (CN) r (X) t] c [M 2 (X) 6] d • zL \ cdot aH_ {2} O \ cdot nM3 {} x A_, in the that: M is a metal ion that forms a precipitate insoluble with the group M 1 (CN) r (X) t, and having at least one water soluble salt; M 1 and M 2 are metal ions of transition that may be the same or different; each X independently represents a group other than cyanide that coordinates with an M 1 or M 2 ion; L represents an organic complexing agent; M 3 x A y represents a soluble salt in metal ion water M3 and anion A; b and c are positive numbers that, together with d, they reflect an electrostatically neutral complex; d is zero or a positive number; x e y are numbers that reflect a salt electrostatically neutral; r is from 4 to 6; t is 0 to 2; Y z, a and n are positive numbers (which can be fractions) indicating the relative amounts of the agent complexing, water molecules and M 3 x A y, respectively and M and M 3 are selected from Zn + 2, Fe + 2, Co + 2, Ni + 2, La + 3 and Cr + 3. 7. A method according to any one of the previous claims, wherein the metal salt in the first  Dissolution is a zinc salt. 8. A method according to claim 7, in the that the metal salt in the impregnation solution is a salt of zinc. 9. A method according to claim 7, in the that the metal salt in the impregnation solution is a salt of chrome, iron or lanthanum. 10. A method according to any of the previous claims, wherein the catalyst containing Metal is represented by the general formula: M_ {b} [M 1} (CN) r (X) t] c [M 2 (X) 6] d • zL \ cdot aH_ {2} O \ cdot nM3 {} x A_, in the that: M is a metal ion that forms a precipitate insoluble with the group M 1 (CN) r (X) t, and having at least one water soluble salt; M 1 and M 2 are metal ions of transition that may be the same or different; each X independently represents a group other than cyanide that coordinates with an M 1 or M 2 ion; L represents an organic complexing agent; M 3 x A y represents a soluble salt in metal ion water M3 and anion A; b and c are positive numbers that, together with d, they reflect an electrostatically neutral complex; d is zero or a positive number; x e y are numbers that reflect a salt electrostatically neutral; r is from 4 to 6; t is 0 to 2; Y z, a and n are positive numbers (which can be fractions) indicating the relative amounts of the agent complexing, water molecules and M 3 x A y, respectively and Anion A is chloride. 11. A method according to any one of the previous claims, wherein the cyanide compounds Metallic have the formula: B u [M 1 (CN) r (X) t] v, in the that: B represents hydrogen or an alkali metal; M 1 is selected from Fe + 3, Fe + 2, Co + 3, Co + 2, Cr + 2, Cr + 3, Mn + 2, Mn + 3, lr + 3, Ni + 2, Rh + 3, Ru + 2, V + 4 and V + 5; r is from 4 to 6; X is an anion selected from halide, hydroxide, sulfate, carbonate, oxalate, thiocyanate, isocyanate, isothiocyanate, C 1-4 carboxylate and nitrite (NO_ {2} -) or an unloaded species selected from CO, H2O and NO; t is 0 to 2 and u and v are integers that reflect a salt electrostatically neutral. 12. A method according to claim 11, in the that M 1 is Co + 3 or Fe + 3. 13. A method according to claim 11 or claim 12, wherein X is NO, NO 2 - or CO. 14. A method according to claim 13, in the that the metal cyanide compound is a compound of water soluble hexacyanocobaltate. 15. A method according to any one of the previous claims, wherein the additional compound is absent. 16. A method according to any one of the claims 1 to 14, wherein the second solution contains an additional compound of formula; B u [M 2 (X) 6] v, in the that: B represents hydrogen or an alkali metal; M 2 is selected from Fe + 3, Fe + 2, Co + 3, Co + 2, Cr + 2, Cr + 3, Mn + 2, Mn + 3, lr + 3, Ni + 2, Rh + 3, Ru + 2, V + 4 and V + 5; X is an anion selected from halide, hydroxide, sulfate, carbonate, oxalate, thiocyanate, isocyanate, isothiocyanate, C 1-4 carboxylate and nitrite (NO_ {2} -) or an unloaded species selected from CO, H2O and NO; Y u and v are integers that reflect a salt electrostatically neutral. 17. A method according to claim 16, in the that M 2 is Co + 3 or Fe + 3. 18. A method according to claim 16 or claim 17, wherein X is NO, NO 2 - or CO. 19. A method according to any one of the previous claims, wherein the complexing agent is select among alcohols, aldehydes, ketones, ethers, amides, nitriles and sulfides. 20. A method according to claim 19, in the that the complexing agent is selected from t-butanol, 1-t-butoxy-2-propanol,  polyether polyols having an equivalent weight of 75-350 and dialkyl ethers of alkylene and polyalkylene glycols 21. A method according to claim 20, in the that the complexing agent is selected from t-butanol, 1-t-butoxy2-propanol,  polyether polyols having an equivalent weight of 125-250 and a dimethyl ether of mono-, di- or triethylene glycol. 22. A method according to claim 21, in the that the complexing agent is selected from t-Butanol and glyme (1,2-dimethoxyethane). 23. A method according to any one of the previous claims, wherein the impregnation solution  It contains a polyether. 24. A method according to claim 7, in the that, in step e) 0.2 to 1.5 moles of metal salt are added per mole of metal cyanide compound and additional compound, which They are used in stage b).